Detergent bar



United States Patent 3,226,330 DETERGENT BAR Raymond Michael Anstett, Hazlet, Null, assignor to Colgate-Palmolive Company, New York, N.Y., a cor poration of Delaware No Drawing. Filed Jan. 7, 1960, Ser. No. 920 4 Claims. (Cl. 252-117) This application is a continuation-in-part of my U.S. patent application S.N. 833,152, now Patent No. 3,076,766.

The present invention relates to a detergent bar containing water soluble soap, certain synthetic detergents and an alkali stable starch.

The improved bar product has excellent washing properties, yields no undispersed curd in hard water and possesses tactile properties, appearance, drying activity and processing characteristics resembling those of the ordinary higher fatty acid soaps. It sloughs even less than a bar of the earlier application mentioned and absorbs less moisture when stored at high humidity.

In accordance with the present invention it has been discovered that such a detergent bar consists essentially of: 8 to alkali metal salt of substantially saturated higher fatty glyceryl sulfuric acid compound; 3 to 10% alkali metal salt of higher acyl amide of an amino lower aliphatic sulfonic acid of 2 to 4 carbon atoms; 45 to 65% soluble alkali metal soap with a major proportion thereof being sodium soap, more than 65% of the soap fatty acid content being saturated fatty acids, and having a predominant amount, over 75%, of the soap fatty acid of 12 to 18 carbon atoms, of which fatty acids to 60% is of 12 to 14 carbon atoms and 75 to is of 16 to 18 carbon atoms; 2 to 10% alkali stable starch; 6 to 16% moisture; and less than 7% total content alkali metal sulfate an alkali metal chloride. In preferred formulations there are employed 10 to 17% of sodium salt of substantially saturated higher fatty acid monoglyceride sulfate; 4 to 8% sodium salt of higher acyl amide of N-methyl taurine; to soluble sodium soap having more than of its fatty acid content of saturated fatty acids, over 85% of the soap fatty acid being of 12 to 18 carbon atoms, of which fatty acids 30 to 50% is of 12 to 14 carbon atoms and 70 to 50% is of 16 to 18 carbon atoms; 3 to 7% alkali stable starch; 8 to 14% moisture; and less than 5% total content of sodium sulfate and sodium chloride.

The alkali metal salt of substantially saturated higher fatty glyceryl sulfuric acid compound is made by any of various known techniques in which a higher fatty radical is attached to a glyceryl stem converted to a corresponding sulfuric acid compound. The detergent contains only one sulfuric acid type group and only one higher fatty radical. The sulfuric acid compound may be either a sulfate or sulfonate and the fatty portion may be of 10 to 18 carbon atoms, preferably in straight line configuration, attached to the glyceryl stem through either a carbonyl or ether linkage. As examples of this specific type may be mentioned the sodium salt of coconut oil fatty acids monoglyceride sulfate, wherein the coconut oil may be hydrogenated if so desired, sodium lauryl ether glyceryl sulfonate, sodium and potassium hydrogenated talloW fatty acids, monoglyceride sulfates, sodium myristyl monoglyceride sulfonate and sodium palmityl ether glyceryl sulfate, to name a few of these suitable detergents. These compounds may be used in mixtures if so desired. Some of this type of detergent, e.g., sodium and potassium lauryl 3,226,330 Patented Dec. 28, 1965 ice ether glyceryl sulfonate, possess sufficiently good curd dispersion properties to allow replacement of some amide sulfonate constituent too.

The alkali metal salt of higher acyl amide of amino lower aliphatic sulfonic acid is one in which the acyl group is of 12 to 18 carbon atoms. The amino aliphatic sulfonic acid portion of the molecule may have a lower alkyl radical attached to the amino nitrogen. The total of carbon atoms in the lower aliphatic stern connecting the amino and sulfonic acid groups and in said lower alkyl radical may be from 2 to 4. The lower alkyl of the connecting alkyl stem is of 2 to 3 carbon atoms and the lower alkyl which may be attached to the nitrogen may be of 1 to 2 carbon atoms. Among the compounds of this type which may be used in the disclosed detergent bars are sodium higher acyl amide of N-methyl taurine in which the acyl grouping is a mixture of palmitoyl and stearoyl, sodium oleic acid amide of N-methyl taurine and sodium hydrogenated coconut oil fatty acids amide of propane sulfonic acid.

As is seen from the above examples it is preferred to use those compounds having 3 carbon atoms in the lower amino sulfonic acid portion of the molecule.

The water soluble alkali metal soap of the invented compositions contains a major proportion of sodium soap,

usually over The soap fatty acid content is 65 or more saturated. The soap also consists predominantly of 12 to 18 carbon atom molecules, preferably and more being of this chain length. These soaps comprise the previously specified proportions of fatty acid soaps of 12 to 14 carbon atoms and of others of 16 to 18 carbon atoms. Such materials may be made by combining in proper proportions known soap making oils of known fatty acid analyses. For example, it has been found that coconut oil or hydrogenated coconut oil may be mixed with tallow in the soap kettle in such proportions as to result in soaps of the type needed in the present detergent bar. Thus, it is possible to make such a soap by mixing one part by weight of coconut oil with two parts by weight of commercial tallow, and similarly, a satisfactory soap can be produced from four parts coconut oil and one part tallow. Within the boundaries of such compositions are other satisfactory soap mixtures, the preferred embodiment of which is one made from equal parts of these oils. Instead of coconut oil and tallow, other suitable sources of fatty acids or glycerides may be substituted to obtain a soap mixture of the type described.

The alkali stable starch does not hydrolyze, discolor or change chemically to an objectionable extent in the presence of the soap, synthetic detergents and moisture of combination detergent bars. When subjected to the test of Schoch and Jensen, as described at pages 679, 680 of Chemistry and Industry of Starch, 2nd ed. (1950), by Ralph W. Kerr, the maximum alkali number of a suitable alkali stable starch should be about 10, preferably 5 or less. However, the ultimate test of the starch is whether it changes objectionably in the bar composition and this should be considered in conjunction with the alkali number indicated by the test mentioned in evaluating a starch to be used in these bars.

The stable starch used may be obtained from corn, potatoes or other known source. Usually the starch'containing plant is bred or selected for inherent stability, which stability is then increased by subsequent treatment, modification or fractionation. One way to improve stability i by removing proteinaceous materials, which appear to promote the development of color changes. In one such process both protein and ash are removed from a macerated starch-bearing grain of good alkali stability and the resulting starch is re-tested to assure that an alkali number of about 5 has been attained.

It has been noted that amylopectin, a starch fraction, may be used in the combination detergent bars disclosed. Unlike most natural untreated starches, amylopectin is free of amylose, usually a minor constituent of starch. In most other starches there is up to 30% amylose, although some will only contain as little as 2-5 thereof. In view of their common structure, both amylopectin and other treated starches, as well as modified starches are included within the generic designation of starch in this specification and in the claims. Both amylopectin and starch readily form ethers, esters and other derivatives. Such compounds are often more soluble than the starting material and also are useful as substitutes therefor in the present compositions.

The combination of synthetic detergents, soap and starch in the proportions disclosed, together with the proper amount of moisture and minimum content of sodium sulfate and sodium chloride, preferably less than 5%, results in a composition which can be made into bar form in substantially the manner employed to make soap cakes and which possesses excellent performance characteristics. It is an exceptionally satisfactory foaming detergent bar for bath and facial use and is excellent insofar as curd dispersion or scum formation in hard water is concerned although similar formulations made from different soaps and detergents do cause objectionable curd production. The present composition dries relatively fast to an attractive appearance.

It also has a lesser tendency to slough or develop smeary surface gels after wetting or when standing in a wet soap dish. Another significant advantage is low moisture ab sorption and less softening in high humidity storage. These latter two advantages are of great importance to the discriminating consumer and make the improved bar superior in these respects (as well as being generally preferred by the consumer) over similar formulas containing alkyl benzene sulfonate detergent in place of starch.

The present detergent bars are the products of interacting detergent components present in the proportions specified. Although each component affects the properties of the others, within the formulas disclosed it is possible to set forth a set of principles to assist one skilled in the detergent art in manufacturing the best detergent bars. The monoglyceride sulfate or other suitable sulfuric acid compound aids in the production of a bar having excellent foaming properties. This type compound also exhibits curd dispersing activity, but in itself, in the quantities employed, usually i not sufficiently effective in this respect. The amide of amino sulfonic acid is an excellent curd disperser in these formulas and has foaming powers. The soap employed in the present compositions has been found to result in producing less soap curd in water containing calcium and magnesium ions than soaps of lesser saturation and greater content of 16 and 18 carbon atoms. Because of this behavior it is possible to make a bar of the relatively low synthetic detergent content range given and still obtain a degree of foaming and curd dispersion formerly associated principally with products of higher synthetic detergent: soap ratios. The present soaps also produce more foam than does ordinary soap in bars containing the disclosed mixture of synthetic detergents, yielding a quicker, richer and creamier lather. As moisture content is increased, the bar tends to become softer, more soluble and to slough more readily, although the presence of the starch allows for an increased tolerance of moisture, while below a minimum water content the composition is very difficult or impossible to mill and plod.

The starch in these bars also decreases sloughing and absorption of atmospheric moisture. Surprisingly, although starch is not a foaming agent or detergent, bars of these formulas made with it replacing alkyl benzene sulfonate are as good in foam and lathering properties as those containing the additional detergent and also are of satisfactory lubricity or slip. With such unexpected effects of the starch on these bars it is found possible to decrease the alkyl benzene sulfonate or even to remove it completely from the formula. Decrease of alkyl aryl sulfonate is found beneficial and is accompanied by lowered bar solubility in water and reduced moisture absorption and gelation. It is preferred to keep the alkyl aryl sulfonate content at a minimum, about 1% or less of the bar. The presence of sodium sulfate and sodium chloride in amounts in excess of the limit given tends to cause crystallization and sometimes produces in the detergent bar a graininess which is objectionable to the user.

In formulating detergent bars according to the teaching of this specification, amounts of components may be adjusted within the ranges given but best results are obtained by selection of proportions in accordance with the following principles. If the amount of amide sulfonate compound is near the maximum, that of glyceryl sulfuric salt may be decreased, allowing use of an amount thereof sufiicient to yield a good foaming product in conjunction with the formula amounts of other detergent and starch employed. On the other hand, if a maximum of glyceryl sulfuric salt is used, less amide is needed for satisfactory curd dispersion. The amide compound is a more effective curd dispersant and the glyceryl sulfuric salt is a better foaming agent in these compositions. A decrease in total synthetic detergent concentration permits use of more lower molecular weight soap (made from fatty acids of 12 and 14 carbon atoms) and an increase of such detergents indicates that more of the higher soaps may be added to improve bar hardness and decrease any excessive solubility. The alkali metal of the detergents and soaps is preferably sodium but potassium compounds are also useful. The amounts of sodium and potassium soaps and detergents should be chosen to obtain a bar of satisfactory hardness and solubility. The starch present should be enough to decrease slough and moisture absorption but not so much as to make the bar rough to the hands and skin. Other considerations in formulation, similar to those recited above, will be apparent to one of skill in the art from the disclosure.

Although good foaming, curd dispersion, slip, appearance and detergency are desirable, even very important properties of detergent bars, those products intended for personal use should also possess other attributes to make them acceptable to the consumer. Among the more important of these properties are those of low moisture absorption, speedy drying and, associated therewith, aesthetically pleasing appearance and tactile properties of a wetted bar. The ordinary fatty acid soaps, being water soluble, dissolve to some extent when in contact with water in the soap dish or on the wash stand. In addition to dissolving some of the soap at the surface of the bar, water contacting the bar is absorbed by the soap and forms with it a soft gel-like surface layer which is easily removed and deposited on the soap dish or hands of the user. Although the soap gel described is undesirable, soap dries and hardens fairly quickly and therefore a cake of soap is normally of acceptable hardness in ordinary usage, provided that it is not stored continuously in water and if it is given suflicient time to drain and dry between washings.

The large majority of synthetic detergents has a greater affinity for water than soap and often such products dissolve too rapidly to be useful toilet bar detergents by themselves. When mixed with soap in amounts sufficient to yield a curd-free washing solution of satisfactory foaming power and detergency they aggravate the tendency of the bar to dissolve and increase the amount of surface softening and gelatin. Sometimes this leads to unacceptable degrees of sloughing and unsightly deposits of gel in the soap dish. In some formulas the synthetic detergent decreases drying rate of the soap, giving a product that appears wet and jellified at the surface for comparatively long periods after usage and sometimes it causes the bar to take up moisture from the atmosphere. The present detergent bar is exceptional in that it is of sufficient solubility and excellent performance characteristics but does not exhibit either excessive sloughing and gel formation nor does it dry slowly or absorb atmospheric moisture. In comparative tests the invented product dried about as well as commercial toilet soap cakes and did not absorb an objectionable amount of moisture. Possibly as important as the improved drying rate of this product is the fact that the bar not only dries to an attractive surface but also appears to the consumer to be dry.

In the composition of this invention there may be incorporated in minor amounts various adjuvant materials designed to contribute specific properties to the bar. Included among this group of materials are: bactericides, e.g., hexachlorophene, trichlorcarbanilide, halosalicyl haloanilides, mercurials; perfumes; pigments and opacifying agents, e.g., titanium dioxide; dyes and colorants; brighteners, e.g., aminostilbenes; sequestrants, e.g., tetrasodium ethylene diamine tetraacetate; antioxidants and stabilizers, e.g., sequestrants for metal impurity catalysts, stannic chloride, stannous chloride, sodium metabisulfite, ditertiary-butyl para cresol; emollients, e.g., lanolin. The amount of adjuvant should be snfiicient to impart the desired activity but not to substantially adversely affect the bar properties. Also present in these bars there will sometimes be found small quantities of so-called ether solubles, which are usually unreacted oils or fats or by-product oils, fatty acids or other compounds from the manufacture of the detergents and soaps. As with some of the adjuvants it is preferred to hold this ingredient to a practical minimum consistent with detergent manufacturing considerations but small amounts, e.g., 14%, do not usually interfere with production of a satisfactory bar.

The bars of this invention may be made according to the usual methods employed in the manufacture of corresponding soap products with only minor adjustments known to those skilled in the art of making combination soap-detergent bars. The consitituents of the formula are preferably mixed in the crutcher and dried to proper mois ture content but may also be blended in the amalgamator. If desired, neutralization or other reactions may be effected in the crutcher. For example, the acylated amino sulfonic acid, together with unreacted or excess fatty acid, may be crutcher neutralized. Drying of the crutched detergent mixture may be by known tunnel-, flash-, sprayor film-drying techniques, of which the latter, utilizing an APV or Rosenblad drier, is preferred. In either the crutching or part of the drying operation the starch is hydrated to gel form. In the amalgamation step the desired moisture content of the final product may be further adjusted by any of various known methods. Water may be added to the formula constituents, if needed, or one or more of the components may be added in water solution or slurry. Usually the minor adjuvants of the bar composition are blended with the detergents in the amalgamator. The formula is then milled to form a homogeneous chip which is compacted and extruded, usually by a soap plodder. After plodding, the extruded bar is cut to lengths and pressed in a conventional soap press, such as a standard high speed, duplex press in which opposed dies form the soap cake in a rotatable die box.

The following examples are given to illustrate the invention but are not to be regarded as limiting. All amounts and percentages in the specification and claims will be by weight unless otherwise indicated.

6 Example I Percent Sodium hydrogenated coconut oil fatty acids monoglyceride sulfate 15 Sodium higher fatty (mixed C C acid amide of N-methyl ta-urine 5 Sodium soap (1:1 coconut oilztallow ratio) 55.4 Alkali stable starch 5 Sodium sulfate 0.9 Sodium chloride 1.7 Moisture 12 Other ingredients (bactericide, perfume, pigment, opacifier, color solution, unreacted and by-product ether soluble oils, fatty acids, etc.)

1 active starch, 325 mesh, designated NL, manufac tured by Stein, Hall 8; Co., Inc., New York, N.Y. at is made from a corn starch (about 76% amylopectin), which was selected for stability to alkali, was ground to a wet meal and was washed free of protein and ash. After production the starch is tested for alkali stability according to the method of Schoch and Jensen as described at pages 679, 680 of Chemistry and Industry of Starch, 2nd ed. (1950), by Ralph W. Kerr. It has an alkali number of 455, which is indicative of good alkali stability. Alkali stable water soluble starches should have alkali numbers less than about 0, preferably even less than 5, and should have low proteinaeeous content.

The synthetic detergents, starch and soap are mixed together (with accompanying sodium salts and ether solubles) in a crutcher to form an aqueous solutiondispersion or slurry. Small proportions of alcohol (ethanol, isopropanol) may be added in the crutcher to keep the starch from prematurely jelling so much as to prevent adequate mixing and easy pumping. After drying to the indicated moisture content in a plate-type film drier, the chips resulting are mixed in an amalgamator with the desired adjuvants. The amalgamated composition is then milled three times to homogeneity, plodded in a vacuum plodder, cut and pressed in essentially the same manner employed for making soap.

Bars made were examined for various properties mdicative of utility of the product in hard and soft water, among which properties were lather and foam, hand washing, curd dispersion, drying characteristics, slough, abrasion resistance, moisture absorption and appearance. They produced essentially no undispersed curd, gave a copious, creamy lather, dried about as fast as soap alone, and were rated as excellent bar detergents. In several of the above properties the bar was compared directly with similar bars made without starch, an equal weight of anionic synthetic detergent, sodium dodecyl benzene sulfonate derived from propylene tetramer alkylate being used instead. The bar of this example was decidedly superior in being of a lesser tendency to absorb moisture from the atmosphere, gaining only 60% as much mo sture as the other bar, even when stored at 88% humidity for 9 days. Thus, the invented bar remains harder under such humid storage conditions, excessive moisture absorption being a cause of objectionable softening of detergent bars. In a test for sloughing, measured by partially immersing a bar in water for 17 hours, then wiping off soft surface gel and measuring weight loss, the bar of this example sloughs less than the non-starch bar mentioned above.

In the formula given, either all or part of the sodium hydrogenated coco-monoglyceride sulfate may be replaced by others of the higher fatty glyceryl sulfuric acid products described elsewhere, in accordance with the teachings of this specification. The resulting products will also be excellent bar detergents.

The N-methyi tauride of this formula may be replaced either wholly or in part by other amides of amino lower aliphatic sulfonic acids previously mentioned. When such substitution is made and the teachings of this specification are followed the bar resulting will produce little 7 or no undispersed curd and will have the other desired qualities of the above compositions.

The amount of starch used may be from 2 Less than 2% has little appreciable effect and more than about 10% often tends to roughen the bar surface.

Example II Percent Sodium higher fatty acids monoglyceride sulfate Sodium higher fatty acid amide of N-methyl taurine 5 Sodium soap 2 55 Amylopectin 5 Moisture 12 Total alkali metal sulfate and alkali metal chloride 2.6 Other ingredients 5.4

71% saturated fatty acid soap of which 84% is of 12 to 18 carbon atoms, 38% of which is of 12 to 14 carbon atoms and 62% of which is of 16 to 18 carbon atoms.

Ramalln P, 90% active, made by Stein, Hall Co., Inc., New York, N.Y. This is a 325 mesh amylopectin derived from potato starch and separated from amylose by the AV'EBE process. It has an alkali number of about 10.

This detergent bar Was made by the method of Example I. It too, was good in lathering, foam, curd dlspersion, appearance, drying speed, slough properties, detergency, color and odor stability and so forth and was an acceptable bar. Despite the use of less detergent it was the equal of the non-starch bar mentioned in Example I in lathering power and was superior to it in slouglung less and absorbing less moisture under humid atmospheric conditions.

Example III Percent Sodium higher fatty acid monoglyceride sulfate 15 Sodium higher fatty acid amide of N-methyl taurine '(Igepon TE42) Alkali metal sodium soap (1:1 coconut OllitallOW ratio) 55 Alkali stable starch 5 Total sodium sulfate and sodium chloride 3 Moisture 12 Other ingredients 5 Example IV Percent Sodium coconut oil fatty acids monoglyceride sulfate 15 Sodium higher fatty acid amide of N-methyl taurine 5 Sodium dodecyl benzene sulfonate 1 Sodium soap (SO-50 coco-tallow) 53 Amylopectin 6 6 Total sodium sulfate and chloride 3 Moisture 12 Other ingredients 5 Ramalin 1?.

Example V Percent Sodium coconut oil monoglyceride monosulfate 15 Sodium higher fatty acid amide of N-methyl taurine 5 Sodium higher normal alkyl sulfonate 5 Sodium soap (50 coco-50 tallow) 50 Total sodium sulfate and sodium chloride 3 Alkali stable starch (NL) 5 Moisture 12 Others 5 The bars of Examples III-V were made by dry mixing the compositions in an amalgamator, adding the required amount of moisture, milling, plodding and pressing. Bars produced were good and are useful for bath and facial use. All sloughed less than described control bars containing alkyl benzene sulfonate detergent and no starch and all lathered about as well as such contro bars. However, indications are that more than about 1% alkyl benzene sulfonate in the product of Example IV will increase slough and moisture absorption and should not be used. Also, although the alkyl sulfonate detergent does not slough as badly as many other sulfonates, it apparently doesnt improve lathering appreciably and a bar containing the less expensive soap instead performs as well in many respects. Therefore, of the three bars of these examples, that containing only the claimed deter gents and starch is considered to be the best.

Instead of dry mixing, these bars may be made by the wet method disclosed in Examples I and II. In such cases there is less chance of surface roughness developing due to the presence of undispersed starch.

The above invention has been described in conjunction With illustrative examples thereof. It will be obvious to those skilled in the art who read this specification that other variations and modifications of the invention can be made and various equivalents substituted therein without departing from the principles disclosed or going outside the scope of the specifications or purview of the claims.

What is claimed is:

1. A milled and plodded detergent bar consisting essentially of 8 to 20% alkali metal selected from the group consisting of sodium and potassium salt of substantially saturated higher fatty glyceryl sulfuric acid compound, said sulfuric acid compound being a member selected from the group consisting of sulfate and sulfonate compounds, in which the higher fatty group is of 8 to 18 carbon atoms; 3 to 10% alkali metal salt of higher acyl amide of an amino lower aliphatic sulfonic acid of 2 to 4 carbon atoms, said acyl group containing from 12 to 18 carbon atoms and the alkali metal salt is selected from the group consisting of sodium and potassium salts thereof; 45 to 65% soluble alkali metal soap selected from the group consisting of sodium and potassium soap with a major proportion thereof being sodium soap, more than 65% of the soap fatty acid content being saturated fatty acids, and having a predominant amount, over of the soap fatty acid of 12 to 18 carbon atoms, of which fatty acids 25 to 60% is of 12 to 14 carbon atoms and 75 to 40% is of 16 to 18 carbon atoms; 2 to 10% alkali stable starch; 6 to 16% moisture; and having less than 7% total content of alkali metal sulfate and alkali metal chloride.

2. A milled and plodded detergent bar consisting essentially of 8 to 20% sodium salt of substantially saturated higher fatty acid monoglyceride sulfate in which the higher fatty acid group is of 8 to 18 carbon atoms; 3 to 10% sodium salt of higher acyl amide of N-methyl taurine, said acyl group containing from 12 to 18 carbon atoms; 45 to 65% soluble sodium soap, having more than 65% of its fatty acid content of saturated fatty acids and having substantially all of the soap fatty acid of 12 to 18 carbon atoms, of which fatty acids 25 to 60% is of 12 to 14 carbon atoms and 75 to 40% is of 16 to 18 carbon atoms; 2 to 10% alkali stable starch; 6 to 16% moisture; and having less than 5% total content of sodium sulfate and sodium chloride.

3. A milled and plodded detergent bar consisting essentially of 10 to 17% of sodium salt of substantially saturated higher fatty acids monoglyceride sulfate in which the higher fatty acids group is of 8 to 18 carbon atoms; 4 to 8% sodium salt of higher acyl amide of N-methyl taurine in which the acyl group is of 12 to 18 carbon atoms; 50 to 60% soluble sodium soap, having more than 70% of its fatty acid content of saturated fatty acids and having substantially all, over of the soap fatty acid of 12 to 18 carbon atoms, of which fatty acids 30 to 50% is of 12 to 14 carbon atoms and 70 to 50% is of 16 to 18 carbon atoms; 3 to 7% alkali stable starch; 8 to 14% moisture; and having less than total content of sod um sulfate and sodium chloride.

4. A milled and plodded detergent bar consisting essen tially of to 17% of sodium salt of substantially saturated higher fatty acids monoglyceride sulfate in which the higher fatty acids group is of 8 to 18 carbon atoms and is derived from coconut oil; 4 to 8% sodium salt of higher acyl amide of N-methyl taurine in which the acyl group is substantially all of 16 to 18 carbon atoms; to soluble sodium soap derived from a mixture of tallow and coconut oil, having more than of its fatty acid content of saturated fatty acids and having substantially all, over of the soap fatty acid of 12 to 18 carbon atoms, of which fatty acids 30 to 50% is of 12 to 14 carbon atoms and 70 to 50% is of 16 to 18 carbon atoms; 3 to 7% alkali stable starch having an alkali number of about 10 or less; 8 to 14% moisture; and having less than 5% total content of sodium sulfate and sodium chloride.

References Cited by the Examiner UNITED STATES PATENTS 2,438,169 3/1948 Hoyt 252-121 2,714,093 7/ 1955 Blumenthal -a 252--121 XR 2,749,315 6/ 1956 Faier 252-417 2,781,320 2/1957 Jelinek et a1 252-421 2,894,912 7/1959 Geitz 252-421 2,982,735 5/1961 Blinka et al 252- 121 2,988,511 6/1961 Mills et a1. 252121 FOREIGN PATENTS 796,627 6/ 1958 Great Britain.

JULIUS GREENWALD, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,226,330 December 28, 1965 Raymond Michael Anstett It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 7, line 19, for "84%" read 94% in the grant (only) columns 9 and 10 were inadvertently omitted and the data contained therein should appear as shown below:

carbon atoms; 3 to 7% alkali stable starch; 8 to 14% moisture; and having less than total content of sodium sulfate and sodium chloride.

4. A milled and plodded detergent bar consisting essentially of to 17% of sodium salt of substantially saturated higher fatty acids monoglyceride sulfate in which the higher fatty acids group is of 8 to 18 carbon atoms and is derived from coconut oil; 4 to 8% sodium salt of higher acyl amide of N-methyl taurine in which the acyl group is substantially all of 16 to 18 carbon atoms; to soluble sodium soap derived from a mixture of tallow and coconut oil, having more than of its fatty acid content of saturated fatty acids and having' substantially all, over of the soap fatty acid of 12 to 18 carbon atoms, of which fatty acids 30 to 50% is of 12 to 14 carbon atoms and 70 to 50% is of 16 to 18 carbon atoms; 3 to 7% alkali stable starch having an alkali number of about 10 or less; 8 to 14% moisture; and having less than 5% total content of sodium sulfate and sodium chloride,

References Cited by the Examiner UNITED STATES PATENTS 2,438,169 3/1948 Hoyt 252-121 2,714,093 7 1955 Blumenthal --252-121 XR 2, 749,315 6/1956 Faier --252-117 2,781,320 2/1957 Jelinek et al, --252-121 2,894,912 7/1959 Geitz --252-121 2,982,735 5/1961 Blinka et al, --252-121 2, 988, 511 6/1961 Mills et a1 -2S2-l21 JULIUS GREENWALD, Primary Examiner.

Signed and sealed this 12th day of September 1967.

(SEAL) Attest:

EDWARD J. BRENNER Commissioner of Patents ERNEST W. SWIDER Attesting Officer 

1. A MILLED AND PLODDED DETERGENT BAR CONSISTING ESSENTIALLY OF 8 TO 20% ALKALI METAL SELECTED FROM THE GROUP CONSISTING OF SODIUM AND POTASSIUM SALT OF SUBSTANTIALLY SATURATED HIGHER FATTY GLYCERYL SULFURIC ACID COMPOUND, SAID SULFURIC ACID COMPOUND BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF SULFATE AND SULFONATE COMPOUNDS, IN WHICH THE HIGHER FATTY GROUP IS OF 8 TO 18 CARBON ATOMS; 3 TO 10% ALKALI METAL SALT OF HIGHER ACYL AMMIDE OF AN AMINO LOWER ALIPHATIC SULFONIC ACID OF 2 TO 4 CARBON ATOMS, SAID ACYL GROUP CONTAINING FROM 12 TO 18 CARBON ATOMS AND THE ALKALI METAL SALT IS SELECTED FROM THE GROUP CONSISTING OF SODIUM AND POTASSIUM SALTS THEREOF; 45 TO 65% SOLUBLE ALKALI METAL SOAP SELECTED FROM THE GROUP CONSISTING OF SODIUM AND POTASSIUM SOAP WITH A MAJOR PROPORTION THEREOF BEING SODIUM SOAP, MORE THAN 65% OF THE SOAP FATTY ACID CONTENT BEING SATURATED FATTY ACIDS, AND HAVING A PREDOMINANT AMOUNT, OVER 75%, OF THE SOAP FATTY ACID OF 12 TO 18 CARBON ATOMS, OF WHICH FATTY ACIDS 25 TO 60% IS OF 12 TO 14 CARBON ATOMS AND 75 TO 40% IS OF 16 TO 18 CARBON ATOMS; 2 TO 10% ALKALI STABLE STARCH; 6 TO 16% MOISTURE; AND HAVING LESS THAN 7% TOTAL CONTENT OF ALKALI METAL SULFATE AND ALKALI METAL CHLORIDE 